JPH041201A - Production of fine polymer bead having heat sensitive characteristic - Google Patents
Production of fine polymer bead having heat sensitive characteristicInfo
- Publication number
- JPH041201A JPH041201A JP10249990A JP10249990A JPH041201A JP H041201 A JPH041201 A JP H041201A JP 10249990 A JP10249990 A JP 10249990A JP 10249990 A JP10249990 A JP 10249990A JP H041201 A JPH041201 A JP H041201A
- Authority
- JP
- Japan
- Prior art keywords
- surfactant
- solution
- aqueous solution
- concentration
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 34
- 239000011324 bead Substances 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 239000004094 surface-active agent Substances 0.000 claims abstract description 18
- 239000000693 micelle Substances 0.000 claims abstract description 15
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 13
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 5
- 238000004090 dissolution Methods 0.000 claims abstract description 4
- 229920001519 homopolymer Polymers 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- -1 acrylamide compound Chemical class 0.000 abstract description 9
- 239000000243 solution Substances 0.000 abstract description 8
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000011325 microbead Substances 0.000 abstract description 4
- 239000003463 adsorbent Substances 0.000 abstract description 3
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- 239000002537 cosmetic Substances 0.000 abstract description 3
- 239000003405 delayed action preparation Substances 0.000 abstract description 3
- 238000011282 treatment Methods 0.000 abstract description 2
- 125000002091 cationic group Chemical group 0.000 abstract 2
- 230000002209 hydrophobic effect Effects 0.000 abstract 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 abstract 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000839 emulsion Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 6
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229940035044 sorbitan monolaurate Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- YXMISKNUHHOXFT-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) prop-2-enoate Chemical compound C=CC(=O)ON1C(=O)CCC1=O YXMISKNUHHOXFT-UHFFFAOYSA-N 0.000 description 1
- WLPAQAXAZQUXBG-UHFFFAOYSA-N 1-pyrrolidin-1-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCCC1 WLPAQAXAZQUXBG-UHFFFAOYSA-N 0.000 description 1
- NTBSOSCZKLTOPF-UHFFFAOYSA-N 2-methyl-n-(3-propan-2-yloxypropyl)prop-2-enamide Chemical compound CC(C)OCCCNC(=O)C(C)=C NTBSOSCZKLTOPF-UHFFFAOYSA-N 0.000 description 1
- JJOYJOCWEDSDOO-UHFFFAOYSA-N 2-methyl-n-(oxolan-2-ylmethyl)prop-2-enamide Chemical compound CC(=C)C(=O)NCC1CCCO1 JJOYJOCWEDSDOO-UHFFFAOYSA-N 0.000 description 1
- YQIGLEFUZMIVHU-UHFFFAOYSA-N 2-methyl-n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C(C)=C YQIGLEFUZMIVHU-UHFFFAOYSA-N 0.000 description 1
- CCIDRBFZPRURMU-UHFFFAOYSA-N 2-methyl-n-propylprop-2-enamide Chemical compound CCCNC(=O)C(C)=C CCIDRBFZPRURMU-UHFFFAOYSA-N 0.000 description 1
- PIRPEUWCTMKABH-UHFFFAOYSA-N 4-methoxy-2-methylidenebutanamide Chemical compound COCCC(=C)C(N)=O PIRPEUWCTMKABH-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 235000016496 Panda oleosa Nutrition 0.000 description 1
- 240000000220 Panda oleosa Species 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- 241000583281 Sugiura Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 206010057040 Temperature intolerance Diseases 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000008543 heat sensitivity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- KKWUACQXLWHLCX-UHFFFAOYSA-N hydron;tetradecan-1-amine;chloride Chemical compound Cl.CCCCCCCCCCCCCCN KKWUACQXLWHLCX-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 1
- XMWVNAQQVRLLSY-UHFFFAOYSA-N n-(1,3-dioxolan-2-yl)-n-methylprop-2-enamide Chemical compound C=CC(=O)N(C)C1OCCO1 XMWVNAQQVRLLSY-UHFFFAOYSA-N 0.000 description 1
- TVWMAGGSNXUSKO-UHFFFAOYSA-N n-(2,2-dimethoxyethyl)-n-methylprop-2-enamide Chemical compound COC(OC)CN(C)C(=O)C=C TVWMAGGSNXUSKO-UHFFFAOYSA-N 0.000 description 1
- YLQHOUDDHYMERA-UHFFFAOYSA-N n-(2-ethoxyethyl)prop-2-enamide Chemical compound CCOCCNC(=O)C=C YLQHOUDDHYMERA-UHFFFAOYSA-N 0.000 description 1
- IRMNYAOVVDEOKP-UHFFFAOYSA-N n-(3-methoxypropyl)-2-methylprop-2-enamide Chemical compound COCCCNC(=O)C(C)=C IRMNYAOVVDEOKP-UHFFFAOYSA-N 0.000 description 1
- RWJGITGQDQSWJG-UHFFFAOYSA-N n-(3-methoxypropyl)prop-2-enamide Chemical compound COCCCNC(=O)C=C RWJGITGQDQSWJG-UHFFFAOYSA-N 0.000 description 1
- SRTKONRYKAKQGQ-UHFFFAOYSA-N n-(methoxymethyl)-2-methylidenepentanamide Chemical compound CCCC(=C)C(=O)NCOC SRTKONRYKAKQGQ-UHFFFAOYSA-N 0.000 description 1
- DDRUQPHOCBOBDC-UHFFFAOYSA-N n-[3-(2-methoxyethoxy)propyl]prop-2-enamide Chemical compound COCCOCCCNC(=O)C=C DDRUQPHOCBOBDC-UHFFFAOYSA-N 0.000 description 1
- FIBUWQFQYAAXHD-UHFFFAOYSA-N n-cyclopropyl-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NC1CC1 FIBUWQFQYAAXHD-UHFFFAOYSA-N 0.000 description 1
- LCXIFAOALNZGDO-UHFFFAOYSA-N n-cyclopropylprop-2-enamide Chemical compound C=CC(=O)NC1CC1 LCXIFAOALNZGDO-UHFFFAOYSA-N 0.000 description 1
- ZIWDVJPPVMGJGR-UHFFFAOYSA-N n-ethyl-2-methylprop-2-enamide Chemical compound CCNC(=O)C(C)=C ZIWDVJPPVMGJGR-UHFFFAOYSA-N 0.000 description 1
- ZOTWHNWBICCBPC-UHFFFAOYSA-N n-ethyl-n-methylprop-2-enamide Chemical compound CCN(C)C(=O)C=C ZOTWHNWBICCBPC-UHFFFAOYSA-N 0.000 description 1
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 1
- COYVWKMZTCAFHO-UHFFFAOYSA-N n-methyl-n-propan-2-ylprop-2-enamide Chemical compound CC(C)N(C)C(=O)C=C COYVWKMZTCAFHO-UHFFFAOYSA-N 0.000 description 1
- RGNKVBUBMHKKJP-UHFFFAOYSA-N n-methyl-n-propylprop-2-enamide Chemical compound CCCN(C)C(=O)C=C RGNKVBUBMHKKJP-UHFFFAOYSA-N 0.000 description 1
- WDFKEEALECCKTJ-UHFFFAOYSA-N n-propylprop-2-enamide Chemical compound CCCNC(=O)C=C WDFKEEALECCKTJ-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- ZIWRUEGECALFST-UHFFFAOYSA-M sodium 4-(4-dodecoxysulfonylphenoxy)benzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCOS(=O)(=O)c1ccc(Oc2ccc(cc2)S([O-])(=O)=O)cc1 ZIWRUEGECALFST-UHFFFAOYSA-M 0.000 description 1
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 1
- OKDWPOPWOQICDL-UHFFFAOYSA-M sodium;(2-nonylphenyl) sulfate Chemical compound [Na+].CCCCCCCCCC1=CC=CC=C1OS([O-])(=O)=O OKDWPOPWOQICDL-UHFFFAOYSA-M 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- ASJUTVUXOMPOQH-UHFFFAOYSA-M sodium;4-octylbenzenesulfonate Chemical compound [Na+].CCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 ASJUTVUXOMPOQH-UHFFFAOYSA-M 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000005307 time correlation function Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、新規な感熱特性を有する微細なポリマービー
ズの製造方法に関するものである。更に〔従来の技術〕
感熱性を有するサブミクロンゲルビーズの製造は、溶媒
一界面活性剤一ブリゲル水溶液からなる逆相懸濁重合に
よった（広瀬美治、網屋毅之、広用能嗣、田中豊一 第
１目高分子ゲル研究討論会資料、３９（１９８９））。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing fine polymer beads having novel thermosensitive properties. Furthermore, [prior art] heat-sensitive submicron gel beads were produced by reverse-phase suspension polymerization consisting of a solvent, a surfactant, and an aqueous solution of Brigel (Miharu Hirose, Takeyuki Amiya, Yoshitsugu Hiroyo, Tanaka et al. Toyoichi, First Polymer Gel Research Discussion Group Materials, 39 (1989)).
溶媒としてはｎ−へ＋サン、界面活性剤としてはソルビ
タンモノラウレートを用いた。ブリゲル水溶液は、Ｎ−
イソプロピルアクリルアミド、イオン化性モノマーであ
るＮ−アクリロイルオキシスクシンイミド、架橋モノマ
ーであるＮ，Ｎ’ −メチレンビスアクリルアミドおよ
び過硫酸アンモニウムである。窒素置換したｎ−ヘキサ
ンにソルビタンモノラウレートを溶かし、開始剤を含む
プリゲル水溶液を注入し、かくはんしたのち小量のテト
ラメチレンジアミンを加え番杏捲行った。この方法では
、流体力学的直径は、膨潤状態では約８００ｎｍ、収縮
状態では２００〜３００ｎｍである。As the solvent, n-he+san was used, and as the surfactant, sorbitan monolaurate was used. Brigel aqueous solution is N-
These are isopropylacrylamide, the ionizable monomer N-acryloyloxysuccinimide, the crosslinking monomers N,N'-methylenebisacrylamide and ammonium persulfate. Sorbitan monolaurate was dissolved in nitrogen-substituted n-hexane, and an aqueous pregel solution containing an initiator was poured into the solution. After stirring, a small amount of tetramethylene diamine was added and rolled up. In this method, the hydrodynamic diameter is approximately 800 nm in the swollen state and 200-300 nm in the contracted state.
非感熱性のナノメータオーダーの超ミクロスヒイア及び
そのコロイドの製造も可能である。デンドリマー（ｄｅ
ｎｄｒｌｍｅｒ） （Ｄ、Ａ、Ｔｏｍａｌｉａ、 ｅ
ｔａｌ、：Ｍａｃｒｏｍｏｌｅｃｌｌｅｓ、 １９．２
４６６（１９８６））や単分子ミクロスヒアー（Ｊ、
Ｋｕｍａｋｉ： Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ、 １
９．２２５８（１９８６））等があるが、これらは、合
成方法が複雑であったり、分離が容易でないし、温度変
化により、粒子の大きさが変わらない。It is also possible to produce non-thermosensitive nanometer-order ultramicroshears and colloids thereof. dendrimer
ndrlmer) (D, A, Tomalia, e
tal, : Macromolecules, 19.2
466 (1986)) and single-molecule microspheres (J.
Kumaki: Macromolecules, 1
9.2258 (1986)), but these have complicated synthesis methods, are not easy to separate, and do not change particle size due to temperature changes.
上記のサブミクロンピースよりも粒径の更に小さな感熱
特性を有する微細なビーズを製造できれば、更に高性能
の診断用マイクロビーズ、徐放化製剤、吸着剤、化粧品
等への用途が期待される。If it is possible to produce fine beads with heat-sensitive properties that are smaller in particle size than the above-mentioned submicron pieces, it is expected that they will be used in higher-performance diagnostic microbeads, sustained-release preparations, adsorbents, cosmetics, and the like.
本発明は、粒径の更に小さな感熱特性を有する微細なポ
リマービーズの製造方法を提供することを目的としてな
されたものである。The present invention was made for the purpose of providing a method for producing fine polymer beads having a smaller particle size and having heat-sensitive properties.
本発明者らは、鋭意研究を重ねた結果、カチオン界面活
性剤あるいはアニオン界面活性剤を臨界ミセル濃度以上
の濃度で添加した感熱性高分子化合物水溶液系では昇温
により高分子は界面活性剤のミセル内で相転移し微粒子
となって析出するため、肉眼では相転移現象が緩慢にな
ってみえる。As a result of intensive research, the present inventors have found that in a heat-sensitive polymer compound aqueous solution system in which a cationic surfactant or anionic surfactant is added at a concentration higher than the critical micelle concentration, the polymer is absorbed by the surfactant as the temperature rises. Since the particles undergo a phase transition within the micelles and precipitate as fine particles, the phase transition phenomenon appears to be slow to the naked eye.
この知見をヒントにして、カチオン界面活性剤あるいは
アニオン界面活性剤を臨界ミセル濃度以上の濃度で添加
したその単独重合体が親水性−疎水性熱可逆的溶解特性
を呈するアクリルアミド系ビニル化合物と架橋剤からな
る水溶液にカチオン界面活性剤あるいはアニオン界面活
性剤を臨界ミセル濃度以上の濃度で添加して均一な水溶
液を調整し、その曇点以上の温度でミセル内共重合させ
た後、メタノールあるいはエタノールを加えミセル構造
を破壊した後、限外濾過膜を用いて界面活性剤を除去す
ることを特徴とする特許
微細なポリマービーズの製造方法により前記課題’−＝
ＥＪ
を達成しう＋−Ｚとを見出し、この知見に基づいて本発
明を完成するに至った。Taking this knowledge as a hint, we developed an acrylamide-based vinyl compound and a crosslinking agent whose homopolymer, to which a cationic surfactant or anionic surfactant is added at a concentration higher than the critical micelle concentration, exhibits hydrophilic-hydrophobic thermoreversible dissolution characteristics. A cationic surfactant or anionic surfactant is added at a concentration higher than the critical micelle concentration to an aqueous solution to prepare a homogeneous aqueous solution, and after copolymerization within the micelles at a temperature higher than the cloud point, methanol or ethanol is added. In addition, the patented fine polymer bead manufacturing method is characterized by destroying the micelle structure and removing the surfactant using an ultrafiltration membrane.
The inventors have discovered that +-Z can achieve EJ, and have completed the present invention based on this knowledge.
本発明で用いるアクリルアミド系ビニル化合物は一般式
％式％
（上式でＲ１はいずれも水素、メチル基、Ｒ２、Ｒ３は
いずれも水素、アルキル基、アルコキシアルキル基であ
る。）
本発明の対象となるその単独重合体が親水性−疎水性熱
可逆的溶解挙動（感熱性）を示すアクリルアミド系ビニ
ル化合物としては、Ｎ−エチルアクリルアミド、Ｎ−ｎ
−プロビルアクリルアミド、Ｎ−ｎ−プロビルメタクリ
ルアミド、Ｎ−イソプロビルアクリルアミド、Ｎ−イソ
プロピルメタクリルアミド、Ｎ−シクロプロピルアクリ
ルアミド、Ｎ−シクロプロピルメタクリルアミド、Ｎ，
Ｎ−ジエチルアクリルアミド、Ｎ−メチル−Ｎ−エチル
アクリルアミド、Ｎ−メチル−Ｎ−ｎ−プロビルアクリ
ルアミド、Ｎ−メチル−Ｎ−イソプロピルアクリルアミ
ド、Ｎ−アクリロイルビベリジン、Ｎ−アクリロイルピ
ロリジン、Ｎ−テトラヒドロフルフリルアクリルアミド
、Ｎ−テトラヒドロフルフリルメタクリルアミド、Ｎ−
メトキシプロピルアクリルアミド、Ｎ−メトキシプロピ
ルメタクリルアミド、Ｎ一エトキシブロビルアクリルア
ミド、Ｎ一エトキシブロピルメタクリルアミド、Ｎ−イ
ンプロポキシプロピルアクリルアミド、Ｎイソプロポキ
シプロビルメタクリルアミド、Ｎエトキシエチルアクリ
ルアミド、Ｎ−エトキンエチルメタクリルアミド、Ｎ−
（２．２−ジメトキシエチル）一Ｎーメチルアクリルア
ミド、Ｎ−１−メチル−２−メトキシエチルアクリルア
ミド、Ｎ−１−メチル−２−メトキシエチルメタクリル
アミド、Ｎ−１−メトキシメチルプロピルアクリルアミ
ド、Ｎ−１−メトキシメチルプロピルメタクリルアミド
、Ｎ−（１，３−ジオキソラン−２−イル）−Ｎ−メチ
ルアクリルアミド、Ｎ−８−アクリロイル−１，４−ジ
オキサ−８−アザスピロ（４，５３デカン、Ｎ−ジ（２
−メトキシエチル）アクリルアミド、Ｎ−２−メトキシ
エチル−Ｎｎ−プロピルアクリルアミド、Ｎ−２−メト
キシエチル−Ｎ−ｎ−エチルアクリルアミド、Ｎ−メト
キシエトキシプロビルアクリルアミド等をあげることが
できる。The acrylamide-based vinyl compound used in the present invention has the general formula % (In the above formula, R1 is hydrogen or a methyl group, and R2 and R3 are all hydrogen, an alkyl group, or an alkoxyalkyl group.) Examples of acrylamide-based vinyl compounds whose homopolymers exhibit hydrophilic-hydrophobic thermoreversible dissolution behavior (heat sensitivity) include N-ethylacrylamide, N-n
-propylacrylamide, N-n-propylmethacrylamide, N-isopropylacrylamide, N-isopropylmethacrylamide, N-cyclopropylacrylamide, N-cyclopropylmethacrylamide, N,
N-diethylacrylamide, N-methyl-N-ethylacrylamide, N-methyl-N-n-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylbiveridine, N-acryloylpyrrolidine, N-tetrahydro Furfuryl acrylamide, N-tetrahydrofurfuryl methacrylamide, N-
Methoxypropylacrylamide, N-methoxypropylmethacrylamide, N-ethoxybropylacrylamide, N-ethoxybropylmethacrylamide, N-impropoxypropylacrylamide, N-isopropoxypropylmethacrylamide, N-ethoxyethylacrylamide, N-ethquin Ethyl methacrylamide, N-
(2.2-dimethoxyethyl)-N-methylacrylamide, N-1-methyl-2-methoxyethylacrylamide, N-1-methyl-2-methoxyethylmethacrylamide, N-1-methoxymethylpropylacrylamide, N- 1-methoxymethylpropyl methacrylamide, N-(1,3-dioxolan-2-yl)-N-methylacrylamide, N-8-acryloyl-1,4-dioxa-8-azaspiro(4,53 decane, N- Ji (2
-methoxyethyl)acrylamide, N-2-methoxyethyl-Nn-propylacrylamide, N-2-methoxyethyl-Nn-ethylacrylamide, N-methoxyethoxypropylacrylamide, and the like.
本発明の架橋剤としては、Ｎ、Ｎ’ −メチレンビスア
クリルアミド、ジビニルベンゼン等の多官能性ビニル化
合物が使用される。架橋剤の使用量はビニル化合物に対
し通常０．０１〜１０重量％である。As the crosslinking agent of the present invention, polyfunctional vinyl compounds such as N,N'-methylenebisacrylamide and divinylbenzene are used. The amount of crosslinking agent used is usually 0.01 to 10% by weight based on the vinyl compound.
重合反応媒体としての水はイオン交換水、蒸留水、上水
等が使用される。Ion-exchanged water, distilled water, tap water, etc. are used as water as a polymerization reaction medium.
重合を開始する方法としては、放射線あるいは電子線を
照射するか、ラジカル重合開始剤の存在下に加熱するか
、光増感剤の存在下光照射するなど通常知られている任
意の方法を用いることができる。本発明で用いられる重
合開始剤は、水溶性ラジカル開始剤であれば、何れも使
用することができる。例えば、過硫酸アンモニウム、過
硫酸カリ、過酸化水素、ｔｅｒｔ−ブチルパーオキシド
等の過硫酸塩や亜硫酸塩、亜硫酸水素塩、硝酸第二セリ
ウムアンモニウム等のレドックス系開始剤、２゜２′
−アゾビス−２−アミジノプロパン塩酸塩、２．２″−
アゾビス−２，４−ジメチルバレロニトリル、４．４’
−アゾビス−４−ンアノバレイン酸及びその塩等の
アゾ化合物をあげることができる。また、上記の開始剤
を２種以上併用することも可能である。ラジカル重合開
始剤の使用量は単量体に対し通常０．０１〜１０重量％
、好ましくは０．０５〜８重量％である。重合温度は、
使用する開始剤及び使用するビニル化合物により変化す
るが、通常Ｏ〜１００℃でかつ生成した感熱性高分子水
溶液の曇点以上の温度である。As a method for initiating polymerization, any commonly known method is used, such as irradiation with radiation or electron beams, heating in the presence of a radical polymerization initiator, or irradiation with light in the presence of a photosensitizer. be able to. As the polymerization initiator used in the present invention, any water-soluble radical initiator can be used. For example, ammonium persulfate, potassium persulfate, hydrogen peroxide, persulfates such as tert-butyl peroxide, sulfites, bisulfites, redox initiators such as ceric ammonium nitrate, 2゜2'
-Azobis-2-amidinopropane hydrochloride, 2.2''-
Azobis-2,4-dimethylvaleronitrile, 4.4'
Examples include azo compounds such as -azobis-4-aneanobalate and its salts. It is also possible to use two or more of the above initiators in combination. The amount of radical polymerization initiator used is usually 0.01 to 10% by weight based on the monomer.
, preferably 0.05 to 8% by weight. The polymerization temperature is
Although the temperature varies depending on the initiator used and the vinyl compound used, the temperature is usually 0 to 100°C and higher than the clouding point of the produced aqueous heat-sensitive polymer solution.
本発明で用いる界面活性剤は、カチオン界面活性剤およ
びアニオン界面活性剤が用いられる。具体的にはカナ１
ン界面活性剤としては、・トリメチルステアリルアンモ
ニウムクロリド［（Ｃｌ８Ｈ３７Ｎ （ＣＨｓ） ｓ］
ＣＩ、 トリメチルセチルアンモニウムクロリド［
（Ｃ５ａＨａ３Ｎ （ＣＨａ） 、３］ ＣＩ、トリメ
チルセチルアンモニウムプロミド［（ＣｓａＨ３３Ｎ
（ＣＨａ） ａｌ Ｂｒ、 トリフチルｎ−テトラ
デシルアンモニウムクロリド［（ＣＩ４Ｈ２ＧＮ （Ｃ
Ｈａ） ３］ Ｃを等カチオン界面活性剤の疎水基の鎖
長がＣＩ２以上の長鎖を有するものが特によく、これ以
外の種類の長鎖のカチオン界面活性剤でもよい。アニオ
ン界面活性剤としてはハードドデシルベンゼンスルホン
酸ナトリウム、ソフトドデシルベンゼンスルホン酸ナト
リウム、４−ｎ−ｔクチルベンゼンスルホン酸ナトリウ
ム等のアルキルベンゼンスルホン酸塩、ドデシルジフェ
ニルエーテルジスルホン酸ナトリウム、ノニルフェノー
ル硫酸エステルナトリウム塩等の硫酸エステル塩、ジオ
クチルスルホこはく酸ナトリウム、ドデシル硫酸ナトリ
ウム等アニオン界面活性剤の疎水基の鎖長がＣＩ２以上
の長鎖を有するものが好適であるが、これ以外の種類の
長鎖のアニオン界面活性剤でもよい。これらのカチオン
界面活性剤の１種または２種以上、アニオン界面活性剤
の１秤または２種以上併用してもよい。これらの界面活
性剤を感熱性高分子化合物水溶液に添加した系では感熱
性高分子化合物が昇温により相転移するが、その際この
高分子の一部が界面活性剤のミセル内で相転移し微粒子
となって析出するため、見かけ上、昇温による相転移現
象が肉眼では緩慢になってみえると考えられる。このよ
うな現象は、短鎖のイオン型界面活性剤や非イオン界面
活性剤を感熱性高分子化合物水溶液に添加した系では現
れない。The surfactants used in the present invention include cationic surfactants and anionic surfactants. Specifically, kana 1
As a surfactant, trimethylstearylammonium chloride [(Cl8H37N (CHs) s]
CI, trimethylcetylammonium chloride [
(C5aHa3N (CHa), 3] CI, trimethylcetylammonium bromide [(CsaH33N
(CHa) al Br, triphthyl n-tetradecylammonium chloride [(CI4H2GN (C
Ha) 3] C-cationic surfactants having a hydrophobic group with a long chain length of CI2 or more are particularly preferred, and other types of long-chain cationic surfactants may also be used. Examples of anionic surfactants include alkylbenzene sulfonates such as hard sodium dodecylbenzenesulfonate, soft sodium dodecylbenzenesulfonate, and sodium 4-nt ctylbenzenesulfonate, sodium dodecyl diphenyl ether disulfonate, and sodium nonylphenol sulfate. Sulfuric ester salts, sodium dioctyl sulfosuccinate, sodium dodecyl sulfate, and other anionic surfactants with hydrophobic groups having a long chain length of CI2 or more are preferred, but other types of long-chain anionic surfactants are preferred. It may also be a drug. One or more of these cationic surfactants and one or more anionic surfactants may be used in combination. In a system in which these surfactants are added to an aqueous solution of a heat-sensitive polymer compound, the heat-sensitive polymer compound undergoes a phase transition as the temperature rises, but at that time, a portion of this polymer undergoes a phase transition within the micelles of the surfactant. Since it precipitates in the form of fine particles, it is thought that the phase transition phenomenon caused by temperature rise appears to be slower to the naked eye. Such a phenomenon does not occur in a system in which a short-chain ionic surfactant or a nonionic surfactant is added to an aqueous solution of a heat-sensitive polymer compound.
また、これらの界面活性剤に感熱性高分子の曇点を著し
く変えることができる物質の添加は好ましくなく、曇点
を著しく変えない物質の添加してもよい。Further, it is not preferable to add a substance that can significantly change the cloud point of the heat-sensitive polymer to these surfactants, but a substance that does not significantly change the cloud point may be added.
カチオン界面活性剤あるいはアニオン界面活性剤を臨界
ミセル濃度以上の濃度で添加した上述のアクリルアミド
系ビニル化合物１種または２種以上からなる水溶液にカ
チオン界面活性剤あ・るいはで添加して均一な水溶液を
調製し、その曇点以上の温度でラジカル共重合させて架
橋構造を持った重合体エマルションを得る。メタノール
あるいはエタノールを加えミセル構造を破壊した後、こ
のような高分子エマルションから限外濾過膜を用いて界
面活性剤を除去することができ、感熱特性を有する微細
なポリマービーズを得ることができる。A cationic surfactant or anionic surfactant is added to an aqueous solution consisting of one or more of the above-mentioned acrylamide vinyl compounds to which a cationic surfactant or anionic surfactant is added at a concentration higher than the critical micelle concentration to form a homogeneous aqueous solution. is prepared and subjected to radical copolymerization at a temperature above its cloud point to obtain a polymer emulsion with a crosslinked structure. After adding methanol or ethanol to destroy the micelle structure, the surfactant can be removed from such a polymer emulsion using an ultrafiltration membrane, and fine polymer beads with thermosensitive properties can be obtained.
本発明のゲルビーズの流体力学的直径Ｄ１１を光子相関
分光法によって求めた。このゲルビーズは、製造条件に
もよるが、膨潤状態では約７５ｎｍ〜１５０ｎｍ、 収
縮状態では約６５ｎｍ〜１１００ｎであり、その分布は
単分散系に近い。このビーズの特徴は、溶媒−界面活性
剤−ブリゲル水溶液からなる逆相懸濁重合による（広瀬
美治、網屋毅之、広用能嗣、田中豊−第１目高分子ゲル
研究討論会資料、３９ （１９８９））方法のビーズ（
流体力学的直径が膨潤状態では約８００ ｎ ｍ、収縮
状態では２００〜３００ｎｍ）と比べはるかに流体力学
的直径Ｄｒ＋が小さい。相転移の様子については、ナノ
メータサイズのポリマービーズでは連続的で、バルクの
ゲルでは不連続であるという大きな違いがみられた。The hydrodynamic diameter D11 of the gel beads of the present invention was determined by photon correlation spectroscopy. These gel beads have a diameter of about 75 nm to 150 nm in a swollen state and a diameter of about 65 nm to 1100 nm in a contracted state, depending on the manufacturing conditions, and their distribution is close to that of a monodisperse system. The characteristics of these beads are based on reverse phase suspension polymerization consisting of a solvent-surfactant-Brigel aqueous solution (Miharu Hirose, Takeyuki Amiya, Yoshitsugu Hiroyo, Yutaka Tanaka - First Polymer Gel Research Discussion Materials, 39 (1989)) method of beads (
The hydrodynamic diameter Dr+ is much smaller than the hydrodynamic diameter (approximately 800 nm in the swollen state and 200-300 nm in the contracted state). There was a major difference in the appearance of the phase transition: it was continuous in the nanometer-sized polymer beads, and discontinuous in the bulk gel.
本発明の新規な感熱特性を有する微細なポリマービーズ
の製造方法に関するものである。本発明によってできる
微細なポリマービーズは、診断用マイクロビーズ、徐放
化製剤、吸着剤、化粧品等としても十分な性能を発揮し
、さらに広範囲の用途が期待される。The present invention relates to a method for producing fine polymer beads having novel thermosensitive properties. The fine polymer beads produced by the present invention exhibit sufficient performance as diagnostic microbeads, sustained release preparations, adsorbents, cosmetics, etc., and are expected to have a wider range of applications.
以下、実施例により本発明を説明するが本発明はこれに
限定されるものではない。The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.
実施例１
キャピラリー栓を付けたＵ字管付の５００ｍ１！の三角
フラスコの中にＮ−イソプロピルアクリルアミド１０．
０４ｇ５ Ｎ、Ｎ’ −メチレンビスアクリルアミド０
．１０ｇ、 蒸留水１５０．１１ｇ。Example 1 500m1 with U-shaped tube with capillary stopper! 10. N-isopropylacrylamide in an Erlenmeyer flask.
04g5 N,N'-methylenebisacrylamide 0
．． 10g, distilled water 150.11g.
、ソフトド舛４侃ベンゼンスルホン酸ナトリウム０．８
４ｇ（６０％水溶液）を加え窒素ガスを３０分間激しく
通じた。ついで過硫酸アンモニウム４３．３ｍｇを加え
、窒素気流下に攪拌しながら６０°Ｃで３時間重合を行
わせる。重合の進行と共に青味がかった色をした重合体
エマルションが生成した。Sodium benzene sulfonate 0.8
4 g (60% aqueous solution) was added and nitrogen gas was vigorously bubbled through for 30 minutes. Then, 43.3 mg of ammonium persulfate was added, and polymerization was carried out at 60°C for 3 hours while stirring under a nitrogen stream. As the polymerization progressed, a bluish-colored polymer emulsion was formed.
このようにして合成された高分子はミセル内に存在する
ので高分子が沈澱しない程度にメタノールを少量づつ加
えて、このミセル構造を破壊したのち、限外濾過膜を用
いて繰り返し処理することで界面活性剤を除去した。電
気型導度゛の測定により重合体エマルション中に界面活
性剤の存在しないことを確認した。Since the polymer synthesized in this way exists in micelles, methanol is added little by little to the extent that the polymer does not precipitate to destroy this micelle structure, and then repeated treatments using an ultrafiltration membrane are performed. Surfactant was removed. The absence of surfactant in the polymer emulsion was confirmed by measuring the electrical type conductivity.
このようにして得られたゲルビーズの流体力学的半径Ｒ
Ｍを光子相関分光法によって測定した。ゲルビーズを含
む水溶液を、２〜５倍に希釈し、５μｍのフィルターを
通して、ＩＸＩＸ５Ｃｍの光散乱用セルに移した。セル
の温度は、２４〜３５℃の範囲で制御した。ディジタル
・コリレータによって得られた時間相関関数を、キュム
ラントの方法でフィツトさせた。得られた平均の拡散定
数から、Ｅｉｎｓｔｅｉｎ−Ｓｔｏｋｅｓの式により、
流体力学的直径Ｉ）ｌを得た。その結果を表１に示す。The hydrodynamic radius R of the gel beads thus obtained
M was measured by photon correlation spectroscopy. The aqueous solution containing gel beads was diluted 2 to 5 times, passed through a 5 μm filter, and transferred to an IXIX5Cm light scattering cell. The temperature of the cell was controlled in the range of 24-35°C. The time correlation function obtained by the digital correlator was fitted using the cumulant method. From the obtained average diffusion constant, according to the Einstein-Stokes formula,
The hydrodynamic diameter I)l was obtained. The results are shown in Table 1.
表１
実施例２
キャピラー祇」栓を付けたＵ字管付の５００ｍ／の三角
フラスコの中にＮ−イソプロピルアクリルアミド９．
７６ｇ、 Ｎ、 Ｎ’ −メチレンビスアクリルア
ミド０．０９５ｇ、 蒸留水１５０．１３ｇ。Table 1 Example 2 N-Isopropylacrylamide 9.
76g, N,N'-methylenebisacrylamide 0.095g, distilled water 150.13g.
、ノニボールＳ−４０（ノニルフェノールＥＯ４モル付
加物硫酸エステルＮａ塩）
ＣｇＨ１ｇＣ６Ｈ４０（ＣＨ２ＣＨ２０）ｎｓ０３Ｎ８
１．６１ｇ（３１％水溶液）を加え窒素ガスを３０分間
激しく通じた。ついで過硫酸アンモニウム４９．６ｍｇ
を加え、窒素気流下に攪拌しなから６（１’ｃで２時間
重合を行わせる。重合の進行と共に青白味がかった色を
した重合体エマルションカ生成した。実施例１と全く同
様にして重合体エマルション中の界面活性剤を除去し、
実施例１と同様な測定を行い流体力学的直径り、と温度
の関係を表１に示す。, Noniball S-40 (nonylphenol EO 4 mole adduct sulfate ester Na salt) CgH1gC6H40 (CH2CH20) ns03N8
1.61 g (31% aqueous solution) was added and nitrogen gas was vigorously bubbled through for 30 minutes. Then ammonium persulfate 49.6mg
was added, and polymerization was carried out at 6 (1'C) for 2 hours while stirring under a nitrogen stream. As the polymerization progressed, a bluish-white polymer emulsion was formed. Removes surfactant in polymer emulsion,
The same measurements as in Example 1 were carried out, and the relationship between the hydrodynamic diameter and temperature is shown in Table 1.
実施例３
キャピラリー栓を付けたＵ字管付の５００ｍ１！の三角
フラスコの中にＮ−イソプロピルアクリルアミド１３．
３５ｇ、Ｎ、Ｎ“ −メチレンビスアクリルアミド０．
１４ｇ、 蒸留水２００．０７ｇ。Example 3 500m1 with U-shaped tube with capillary stopper! 13. N-isopropylacrylamide in an Erlenmeyer flask.
35g, N,N''-methylenebisacrylamide 0.
14g, distilled water 200.07g.
、４−ｎ−オクチルベンゼンスルホン酸ナトリウム０．
７３ｇを加え窒素ガスを３０分間激しく通じた。ついで
過硫酸アンモニウム８．８ｍｇを加え、窒素気流下に攪
拌しなから６０ ’Ｃで３時ｒＪ１重合を行わせる。Ｎ
合の進行と共に白色をした重合体エマルションが生成し
た。実施例１と全く同様にして重合体エマルション中の
界面活性剤を除去し、実施例１と同様な測定を行い流体
力学的直径Ｄｎと温度の関係を表１に示す。, 4-n-octylbenzenesulfonate sodium 0.
73 g was added and nitrogen gas was vigorously bubbled through for 30 minutes. Then, 8.8 mg of ammonium persulfate was added, and rJ1 polymerization was carried out at 60'C for 3 hours while stirring under a nitrogen stream. N
As the polymerization progressed, a white polymer emulsion was formed. The surfactant in the polymer emulsion was removed in exactly the same manner as in Example 1, and the same measurements as in Example 1 were carried out, and the relationship between hydrodynamic diameter Dn and temperature is shown in Table 1.
実施例４
キャピラリー栓を付けたＵ字管付の３００ｍ１！の三角
フラスコの中にＮ−イソプロピルアクリルアミド１０，
００ｇ５ Ｎ、Ｎ’ −メチレンビスアクリルアミド０
．１０ｇ、 蒸留水１５０．０１ｇ。Example 4 300m1 with U-shaped tube with capillary stopper! N-isopropylacrylamide 10,
00g5 N,N'-methylenebisacrylamide 0
．． 10g, distilled water 150.01g.
、ソフトドデシルベンゼンスルホン酸ナトリウム１．６
７ｇ（６０％水溶液）を加え窒素ガスを２時間通じた。, soft sodium dodecylbenzenesulfonate 1.6
7 g (60% aqueous solution) was added and nitrogen gas was passed through the solution for 2 hours.
ついで過硫酸アンモニウム１２．９ｍｇを加え、−１１
気流下に攪拌しなから６０”Ｃで２時間重合を行わせる
。重合の進行と共に真珠色をした重合体エマルションが
生成した。実施例１と全く同様にして重合体エマルショ
ン中の界面活性剤を除去し、実施例１と同様な測定を行
い流体力学的直径り、と温度の関係を表１に示す。Then, 12.9 mg of ammonium persulfate was added, and -11
Polymerization was carried out at 60"C for 2 hours with stirring under a stream of air. As the polymerization progressed, a pearl-colored polymer emulsion was formed. The surfactant in the polymer emulsion was removed in exactly the same manner as in Example 1. The relationship between the hydrodynamic diameter and temperature is shown in Table 1.
特許出願人 工業技術院長 杉 浦 賢 官庁手続 手続補正書 平成２年６月５日Patent applicant: Director of the Agency of Industrial Science and Technology Sugiura wise Government procedures Procedural amendment June 5, 1990
Claims (1)
するアクリルアミド系ビニル化合物の１種または２種以
上と架橋剤からなる水溶液にカチオン界面活性剤あるい
はアニオン界面活性剤を臨界ミセル濃度以上の濃度で添
加して均一な水溶液を調製し、その曇点以上の温度でミ
セル内共重合させた後、使用した界面活性剤を除去する
ことを特徴とする感熱特性を有する微細なポリマービー
ズの製造方法。A cationic surfactant or anionic surfactant is added to an aqueous solution consisting of one or more acrylamide-based vinyl compounds whose homopolymer exhibits hydrophilic-hydrophobic thermoreversible dissolution characteristics and a crosslinking agent at a concentration higher than the critical micelle concentration. Production of fine polymer beads with thermosensitive properties characterized by adding at a concentration to prepare a homogeneous aqueous solution, copolymerizing within the micelle at a temperature above the cloud point, and then removing the used surfactant. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2102499A JPH0735402B2 (en) | 1990-04-18 | 1990-04-18 | Method for producing fine polymer beads having heat-sensitive properties |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2102499A JPH0735402B2 (en) | 1990-04-18 | 1990-04-18 | Method for producing fine polymer beads having heat-sensitive properties |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH041201A true JPH041201A (en) | 1992-01-06 |
| JPH0735402B2 JPH0735402B2 (en) | 1995-04-19 |
Family
ID=14329104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2102499A Expired - Lifetime JPH0735402B2 (en) | 1990-04-18 | 1990-04-18 | Method for producing fine polymer beads having heat-sensitive properties |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0735402B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08333421A (en) * | 1995-04-03 | 1996-12-17 | Nippon Oil & Fats Co Ltd | Phosphorylcholine group-containing polymer aqueous solution and production method |
| CN114272430A (en) * | 2022-01-24 | 2022-04-05 | 科睿驰（深圳）医疗科技发展有限公司 | Thermo-sensitive embolism microsphere and preparation method thereof |
-
1990
- 1990-04-18 JP JP2102499A patent/JPH0735402B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08333421A (en) * | 1995-04-03 | 1996-12-17 | Nippon Oil & Fats Co Ltd | Phosphorylcholine group-containing polymer aqueous solution and production method |
| CN114272430A (en) * | 2022-01-24 | 2022-04-05 | 科睿驰（深圳）医疗科技发展有限公司 | Thermo-sensitive embolism microsphere and preparation method thereof |
| CN114272430B (en) * | 2022-01-24 | 2023-01-24 | 科睿驰（深圳）医疗科技发展有限公司 | Thermo-sensitive embolism microsphere and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0735402B2 (en) | 1995-04-19 |
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